Stilbene dyestuffs and a process for making the same



stuiis concerned is defined by Patented Nov. 2, 1943 STILBENE DYESTUFFS AND A rnocnssroa MAKING THE SAME Ernst Keller, Basel; sswitz fl i'a s o t Gcigy A. -G., Basel, Switzerland, a firm No Drawing. Application January 16,1942, Serial I 1N0. 421,061; In Switzerland November 20, 1940 Claims.

In U. S. PatentNo. 2,226,202 (application Ser. No. 293383, filed Septemberfi, 1-939), there are described metal containing stilbene azo dyestuffs and their manufacture consisting in condensing in various proportions aminoazmbenzene compounds ofthe general formula. 1

- l"; l \-NN-NH2 SOsHor-TlOOH wherein X represents a hydroxyl, alkox or. carboxyl group or asubstituent exchangeable for hydroxyl and. Y represents a hydroxyl or'alkoxy group or, but not at the same time with X, a substituent exchangeablefor hydroxyl, with dinitrostilbene disulfonic acid or dinitro dibenzyl fclisulfonic acid, if desired together with other amino compounds; and" converting the condensa-'- "tion products on the fibre or in substanceinto metal complex compounds.

It has now been found that similar dyestuffs are obtained bycondensing a definite sub-group of aminoazo benzene dyestuffs without sulfonic acid or carboxylic acid groups, alone or simultaneously with other amino compoundswhich may contain az o'groups, especially also together with the aminoazo dyestuffs, described in the U. S.

Patent No. 2,276,202 (application Ser No. 293,483), according tothe processof this patent, with dinitrostilbene or dinitrodibenzyl disulfonic acid, and treating the condensation'products with metal yielding or with oxidising and metal yielding'agents.

The sub-group of theaminoazc benzene dyethe following general formula w 1 OH Y I I wherein Y represents a hydroxyl or alkoxy group.

Both the benzene nuclei may be further appropriately substituted, excepting sulfonic acid and carboxylic acid groups, the sole condition being that the coupling components can only contain substituents in positions which do not render impossible the formation of the aminoazo hen: zene dyestuffs. A

tro-4-chloro-2earnino-l-hydroxybenzene, 3-amino-4:hydroxydiphenyl-sulfone. As coupling components may be mentioned: m-amin'ophenol, 2

aminol-hydroxytoluene, m-a-nisidine, '3-p ropyloxyor 3,-butoxy l-aminobenzene, 2:5-dimethoxy or 2:5-diethoxy aniline, l-amino-2-meth ylr5- methoxy-benzene.- For the condensation of these aminoazo benzene, compounds, as also for the treatment with metal yielding agents all known possibilities of variation come" into consideration With the new dyestuffs an enlargement of the a shade scale of the stilbene dyestuffs is obtained, in addition the dyeings subsequently treatedon the fibre with metal yielding agents, especially copper salts, are characterisedby a substantially improved very good waterfastness;

The present :inventidnis illustrated, butnot limited, by the following examples, wherein the .parts are by weight unless otherwise stated.

' simpl 1 29 parts of the dyestufi, made by acetic acid coupling of diazotised. 4-nitro-2-amino-l-hyldroxybenzene with m-anisidine in the presence of Bsalt, are heated to boiling underreilux with 'lA parts of; dinitrostilbene disulfonate of sodium, 900

:pai'ts ofv water and200 parts of caustic soda lye of 36 Be, in -a.-stirring boiler for 12-15 hours.

After cooling, neutralisation is effected at about 30 C.- with hydrochloric acid,;,the condensation product is completelyprecipitatedwith sodium chloride and filtered.

The dyestuff dissolves with a brown color in "water, with a blue color in concentrated sulfuric acid and'dyes cotton in brown shades, of which the light and water fastness is'increased by subsequent treatment with copper salts.

Th'ecopper compound of the dyestuif is ob- I t'ained for-example, by'dissolving the above dyestuff in 2000 parts of water and 15 parts of 25% ammonia, and allowing at 90 C. a solution of 1 25 parts of crystalline copper sulfate in 100 parts of water and 50 partsof 25% ammonia to flow in and heating forl2 hours to -95 C. The metallisedf compound is isolated in the usual manner by salting out and filtered.

The dried copper complex compound constitutes an: almost black powder which dissolves with a red-brown CQlOratlon in water, with a blue Th aminoazo benzene dyestuffs are produced a by usual processes by coupling o-hydroxydiazo benzene compounds with aniline derivatives substituted in the meta-position by a hydroxyl or alkcxy group. As diazo components may be menticned by way of example: 4-chloro-2-amino-1- hydroxy-benzene benzene, fi nitrc-2 amino-l-hydroxybenzene, 6- nitro-2ramino-4-chloro-l hydroxybenzene, 6nia i -m ahr whrdmrl e n v 5- 1.

l-nitro-Z-arninoJ hydroxycoloration in concentrated sulfuric acid and dyes cotton in light-fast brown shades. a

When in the above exampleonly 23.7 parts insteadof 47.4 parts, of dinitrostilbene disulfonate of sodium acid are used, a similar dyestuff is obtained, of which the coppercomplex compound dyes cotton in somewhat more reddish brown shades. Very similar dyestuffs are obtained with other alkoxy-m-aminophenols, such as for instance 3,-phenetidine, 3-butoxy-l-aminobenzene an so oni presence cine-salt, and 32 parts of the dyestuifsulpha-nilic acidcresidine are condensed with ing heat for 15 hours with 47.4 parts of dinitrostilbene disulfonate of sodium in 500 parts of water and 100 parts of caustic. soda lye of 36 B; isolated in the'usualmanner and, if Q necessary, converted into the copper-compound.

' l The copper complex compoundof the dyestufl 47.4 parts of diniti'ostilbene disulfonate oi'sodiu n" T in the usual manner. v v l It is converted into the copperfcompoiindfas described in Example 1.

i s When dry the latter constitutes a black powder when dry constitutes a violet black powder; it

in 500 parts of water and 100 parts of caustic i i black? red brown m soda lye of 36 B; for 18 hours at boiling -t em- V perature and the condensation product ls isolated water, with a violet coloration in concentrated sulfuricacid dyes cellulose fibres in light- I fast browny' I grey shades.

Example 5 29 parts 01' the dyestufl. 4-nitro-2-am1no-1- hydroxybenzene m-anisidine. (or m-phenetiwhich dissolves with a yellow-brown color in m dine)' and 38.5 parts or the copper compound water, with a violet? color in "concentrated sul- -of-the vdyestufl momma-1-hydroxyhenzene-4-- 'iuric acid' and dyes cotton in lightfast brown sulfonic acid m-anisidine (r m-phenetlfllne) h x v I are'condensedatboilingtemperature ror l5-18 similar dyestufids obtained whenjcondensm an hours with 47.4 of dinltrostllbene did ton"- "tiori is effected for fihours in 'an'autoclave at f ate 0! sodium 111180051 -'v 120-13050, 2z5-diethoxy-ani1ine,'instead of 2:5- parts of caustic soda lye ot 36 B'.; after 0001- dimethoxy-aniline, "gives very similar dyestuffs. ins. n utra sati n is efle ted w th hydr c ri i v V r 5 acid to a weak alkaline reaction. then the prod- Examplei. V 32 parts of the dyestufl 4 mm 2 this 1 hy "'5 is cgnilplftaiprecmtatad with alum "ridean soa Vdroxybenzene 2:5-dimethoxy-aniline :and' 30.5 The dry dye tuff ut t deep brown powp rts of the dyestufi su n der; it dissolves with red brown coloration in wa- 2:5-dimethylbenzene are condensed by boiling in ter concentrated sulfur: fi i g i if i fig 19 22 g 7 an "acid and dyescotton inred brown shades, sub- 335 pals if; 13;; 163p;l0i"ci3;t0a2 'i gfi a p Q rown s a es f V V lye of 36 B. The condensation product is pre- I V Example 6 v cipitated in the knownmanner, fllteredand, if 2 3 necessary, converted into the copper'compound. h i ggz gfig i g fm 1 g When dry the latter constitutes a black powder; m a bnzeh p 'smmmc acid n it dissolves with yellow brown coloration in water, s f w. t bs I with violet coloration in" concentrated sulfuric with 47 4 parts of dmitio sfilbene d m of acid anddye's'cottonin light iast khaki shades, sodium i 1 7 v v parts or water and 80 parts of caus- When the dyestuff,-before metallising, is dis- 40 inc soda I v v ,1 v, we ye 1336 Be isolatedin the usual solved in 800 parts of water and parts of causmanner and converted mto the 'tic soda lye of 36 Beland heated to boiling for pound y 9 one hour with 150 partsof sodiumhypochlorite The copper compound constitutes black pow (12% active chlorine), a dyestufl is obtained of which dissolves m water with brown 1 i which the P complex compound dyes :15 tion and in concentrated sulfuric acid wit h hi ton in somewhat 'morereddlsh khaki shades of 7 imnar fasmess r0 V colorationand dyes cellulose fibres in full, light. 5 P fast brown shades. V v I Example-4 I gyIn the following-Table I areset out further 16 parts of the dyestufl', obtained by weakly -examples of e- W1 obtainable acco din to I acid coupling. of 4 ch10m 2 d1az Lmdmnbenfi no the present invention, whilst there are only given -z'ene with 2:5-dimethoxy aniline, preferably in i-the limitlng cases.- 8 e y e condensation of the presence of p-salt, and parts of the dye- I one or two molecules of the same aminoazo dyestufl" 2-amino-1-hydroxybenzene-4-sulphonio stuff with one molecule of dinitrostilbene disulacid 2:5-dimethoxyaniline orrequivalent parts onic acid: i Table)" laminoam dy Condensation ratln between Shade of the aminoazo' dyeing of the No. V f dyestui! and copper complex i e m components iiiilltl: ales phonic acid 7 tilts-sleazemetastases;- fili$titli ii e" 4-chlov oor 4-bromo 2-o1nino-l-hydrox'ybenzenfi m AnIsid he" on 151 Bluisl brown. rude 2:1 Violet brown 1:1 Dull brown.

2:1 Violet brown. 1:1 Grey brown. 2:1 D0.- do i iii-hinitii'siy sfnlmen: 11 Red browiif A fl 2:1 B o r d e a n x 15L; r 6-nitro-2-amlno-4-chloro-1-hydroxybenzene.. m-Anisidineu n n m 1,233?" 5-111tro-z-amlnod-hydroxybonlone do r. 1:1 D

of another"dialkoxy aniline; such as for example 2:5-diethoxy aniline, are condensed at bol1 In the following Table II are set out condensation products oflmolecule ot each oi-two dlfl'erent aminoazo dyest'ufls withl molecule of dinitrostilbene disu-l-fonic acid. According to the invention the condensation may, however, also be effected in other. suitable proportions between at least 1-. molecule and at most 2 molecules of aminoazo dyestufl' per molecule of dinitrostilbene disulfonic acid.

cules. of the known aromaticamino: compounds there are usedionone" molecule or a compound Selected :froInl the giloup. consisting of dinitilo' stilben'ed'isul'foni'c acid, din itrodi'benzyl di'sul toni'c acid and; p-ni'trotoluene 'sul-i'oni'c fa'cid'; together with other amind compounds whose u's'efor' this condensation is known; at least one molecule of Table II hade of the dyemg of the copper complex com- 2. Aminoazo dyestiiif 'pound on cotton 4-ch1oroamino-l-hytlioxybenze'ue inanisidine.

i-chlOro-Z-amino-l-hydroxybenzene 2:5-dimethoxyaniline.

4-nitr0-2-an1ino-l-hydroxybenzenc iii-anisidine,

Sulf anilic acid 2:S-dimethyl-l-aminobenzene p-Aminoazobenzene p sulfonicacid Sulfanilic acid --v 2:5-dimethoxyani1ine Sulfanilic acid l=amin0 3=m'etliyl fi-metlioxybenzen Sulianilic acid a-naphthylamine p-Arnmoazobeuzene p-sulfonic acid Sulfanilic acid 2:5diine thoxyanilinc1. j; .i

BrownJ run was. a Bordeauzcbrown "Brown.

Reddishbrown;

Brown. I

Reddish brown.

WhatI'clairn is: y 1. In the manufacture of stilbene dyestufis by condensation of dinitrostilbene' disul'f'onic acid; dinitrodibenzyl disulfonic: acidv or p nitrotolu'ene sulionic acid; with aromatic compounds,v which contain. free amino groups, in any desired proportion, in p'resence of caustic alkalies; with or :without the application of pressure; and if desired subsequent treatment of themro'duct's with metal yielding and/or oxidising agents, the improvement wherein instead of up to two molemiles of the. known aromatic; amino: compounds there; are used on one: molecule. of: a compound selected from the group consisting of dinitrostilbene disulfon'ic acid, dinitrodibenzyl disulfonic acid and p-nitrotoluene sulfonic acid at least one molecule of anaminoazobenzeneidyestuif of the formula "without the application: of pressure; and if. de-

sired subsequent treatment of the products with .metal yielding and/or oxidising agents; the improvement wherein instead of up to two molewherein yi means one menisci of the great en .lsisting of on and'alkoxythesotheit substituents an aminoazo benzene dyestuff of the formula wherein Y means one member of the group consisting of OH and alkoxy, the other substituents of the benzene nucleus I being selected from the group consisting. of H, alkyl, halogen, N02 and SO2.Phe, Phemeaning a phenyl nucleus, the other substituents of the benzene nucleus II being selected from the group-consisting of H, alkyl and alkoxy.

3. In the manufacture of stilbene dyestuffs by condensation of dinitrostilbene disulfonic acid, dinitrodibenzyl disulfomc acid, p-nitrotoluene sulfonic acid with aromatic compounds, which contain free amino groups, in any desired proportion,iih' presence-of caustic alkalies, with or without the application of pressure, and if desired. subsequent treatment of the products with metal" yielding and/0r oxidising agents, the improvement wherein instead of the known arematic amino compounds there are used aminoazobenzene dyestuffs of the formulawherein X1 means a substituent selected from the group consisting of H, alkyi', halogen, N02

and SO2;Phe, Phe meaning a phenyl nucleous,.

dinitrodibenzyl disulfonic acid or p-nitrotoluene sulfonic acid with aromatic compounds, which metal yielding and/or oxidising' agents,.=the 1m: movement whereininstead of the known :aro-

"without the applic'ationcf pressure, and' if desteps of condensing one molecular proportion of :contain free .amino groups, in an? desiredproportionQinpresence of caustic alkalies,.-'withor without the application oi pressure, and iridesired subsequent treatmentof the productswith matic amino compounds there is used an amino:- azobenzene dyestuff of the formula wherein'xr means a substituent selected from the densation with dimtmsmbene disulfonic acid of group consisting of H,ralkyl, halogen," NO: and SOzPhe, Phe meaning a phenyl nucleus, and X: means a substituent selected from the group con 1 sistingof H, alkyl and'alkoxy.

5. In the manufacture of stilbene dyestuffs by "2b condensation of 'dinitrostilbene disulfonic acid,

. dinitrod ibenzyl disulfonic acidor p-nitrotol ue'ne sulfonic acid with aromatic compounds, which contain free amino groups, in'any desired pro-" portion, in presence of caustic alkalies, with or sired subsequent treatment of the products with metal yielding and/or oxidizing agents, the irn-j. provement wherein instead of the known aromatic amino compounds there is used an aminoazobenzene dyestuff of the formula v alkyl and alkoxy. v p r 10. The new stilbene dyestuffs fromthe com;

steps of condensing one :niolecularrproportlon'ol and one molecular proportion of product.

9. The new, stilbene dyestufl's fromthe conaminoazobenzene dyestufl on sisting of OH and alkoxy, the other. substitu- V-ents ofthe benzene nucleus I being, selected from the group consisting of H, alkyl; halogen, NO; and SOaPhe, Phe meaning aqphenyl nucleus the other substituents of the benzenenucleus Ill-being selected from the groupe'con'sisting of 'H,

densation with dinitrostilbene disulfonicacld or at least one amino compound-whose-use for this zene dyestuif N: NHZ

NO: X

wherein Xmeans asubstituent selected from the group consisting of H, alkyl and alkoxy.

6. In the manufacture of stilbene dyestuffs, the 40 steps of condensing one molecular proportion of with one molecular proportion of dinitrostilbene 'disulfonic acid and coppering the condensation r "product. r

7. In the manufacture of stilbene dyestufis, the

OH OCH:"

and one molecular proportion of the copper comv 1 pound of the dyestufi with one molecular proportion of dinitrostilbene disulfo'nic acid.

y 8.i'In the manufacture of stilbenedyestufis, the

12. "The new stilbene dyestufls from the {condensation with 'dinitrostilbene disulfonic acid of 'an aminoazobenaene dyestufl of the formula i 0.alkyl wherein Y meansone member or the group consisting of OH and alkoxy 'the other substituents of thebenzene nucleus! being selected from the :group consisting of H,alky1', halogen,-NOrand M 'SO2.Phe, Phe meaning .a phenyl nucleus, the other substituents of the benzene nucleus IIbelng selectedfrom the group consistingof 11. alkyl and alkoxyr I a i 11. The new stilbenedyestuflsi'roin the condensation with dinitrostilbenedisulfonic acid or an aminoazobenzene dyestufl of the formula NH: I

wherein X1 means a substituent; selected from the group consisting of H, alkyl, halogen, NO:

and SOzPhe, Phe meaning a phenyl nucleus. and

X2 means a substituent selected from the group ,7 consisting of H, alkyl andealklox'y. said dyestufl when being copp'ered rharing iimprov'ed water wherein X means a substituent" selected from the I group consisting of H, alkyl and alkoxy', said dyestuff when being copperedhaving improved water fastness. V a

v '13. The new stilbene dyestufl from the conwherein Y means one member of the :roupcbndensation with one molecular proportion of dinitrostilbene disulfonic acid of one molecular proportion of and one molecular proportion of O CH:

said dyestufi when being coppered having improved water fastness.

14. The new stilbene dyestufi from the condensation with one molecular proportion of dinitrostilbene disulfonic acid of one molecular proportion of OH OCH;

and one molecular proportion of glance.

and one molecular proportion of said dyestufi when being coppered having improved water fastness.

ERNST KELLER. 

